Properties Of Supercritical Fluids Research Articles

Numerical Investigation of Thermohydraulic Characteristics in Supercritical CO2 Natural Circulation Loop with Spatially Varying Temperature

Investigation of thermohydraulic characteristics is highly significant for any natural circulation loop (NCL) applications. The physical properties of supercritical fluids are highly sensitive to temperature when they cross pseudo-critical points. In the current study, steady state thermohydraulic characteristics of NCL with a spatially varying temperature distribution on the source along with different orientations of the source and sink are numerically investigated. A three-dimensional rectangular NCL with a uniform diameter and constant length of source and sink is modeled. The temperature of the sink is held constant, while the temperature of the source varies spatially with local maximum and minimum temperatures. The system performance is investigated for four different operating pressures ranging from 8 to 12 MPa. The mass flow rate is observed to increase with increasing operating pressure for all orientations and heat load distribution at the source. The results also indicate that heat transfer degrades when the fluid crosses the pseudo-critical point. It has been noticed that spatially varying temperature distribution has a maximum of 48% heat transfer variation compared to the constant temperature distribution. Furthermore, a source or sink located in the horizontal leg performs better than the vertical leg.

Experimental investigation on pyrolysis products and pore structure characteristics of organic-rich shale heated by supercritical carbon dioxide

The efficient pyrolysis and conversion of organic matter in organic-rich shale, as well as the effective recovery of pyrolysis shale oil and gas, play a vital role in alleviating energy pressure. The state of carbon dioxide (CO2) in the pyrolysis environment of shale reservoirs is the supercritical state. Its unique supercritical fluid properties not only effectively heat organic matter, displace pyrolysis products and change shale pore structure, but also achieve carbon storage to a certain extent. Shale samples were made into powder and three sizes of cores, and nitrogen (N2) and supercritical carbon dioxide (ScCO2) pyrolysis experiments were performed at different final pyrolysis temperatures. The properties and mineral characteristics of the pyrolysis products were studied based on gas chromatography analysis, X-ray diffraction tests, and mass spectrometry analysis. Besides, the pore structure characteristics at different regions of cores before and after pyrolysis were analyzed using N2 adsorption tests to clarify the impact of fracturing degree on the pyrolysis effect. The results indicate that the optimal pyrolysis temperature of Longkou shale is about 430 °C. Compared with N2, the oil yield of ScCO2 pyrolysis is higher. The pyrolysis oil obtained by ScCO2 extraction has more intermediate fractions and higher relative molecular weight. The ScCO2 can effectively improve the pore diameter of shale and its effect is better than that of N2. The micropores are produced in shale after pyrolysis, and the macropores only are generated in ScCO2 pyrolysis environments with temperatures greater than 430 °C. The pore structure has different development characteristics at different pyrolysis temperatures, which are mainly affected by the pressure holding of volatile matter and products blocking. Compared to the surface of the core, the pore development effect inside the core is better. With the decrease in core size, the pore diameter, specific surface area, and pore volume of cores all increase after pyrolysis.

Density fluctuations and transport properties of supercritical carbon dioxide calculated by molecular dynamics simulation near the Widom line

The phenomenon of supercritical pseudo-boiling reveals the anomalous behavior of various physical and chemical properties of supercritical fluids near the Widom line (WL). To explore the regularity of this anomalous behavior, density fluctuations and transport properties of supercritical carbon dioxide are calculated by molecular dynamics (MD) simulation near the WL. The results show that the loci of density fluctuations extremes form ridge lines near the WL with the same trends. The average errors of the ridge lines are only 1.92% for spatial density fluctuation and 2.61% for temporal density fluctuation compared with the WL, respectively. The viscosity and self-diffusion coefficient have inflection points but no extremes near the WL. By comparing the ridge lines formed by the density fluctuations and the inflection points from the transport properties on the phase diagram, it can be found that the ridge lines and inflection points close to the critical point bunch into a straight line along the WL, and gradually diverge away from the critical point, which is similar to the loci of a series of thermodynamic response functions extremes.

Supercritical-Assisted Ball-Milling Synthesis of Multicomponent Si/Fe3O4/C Composites for Outstanding Lithium-Storage Capability

Attributed to high theoretical capacity and abundant reserves, Si/C anodes have been commercialized in lithium-ion batteries (LIBs). However, the shortcomings of poor interfacial compatibility, low rate performance, and bad stability remain to be overcome. In this paper, a facile method for the synthesis of silicon/iron oxide/carbon (Si/Fe3O4/C) composites by ball-milling in a supercritical carbon dioxide (scCO2) fluid medium is proposed. This method utilizes the diffusion characteristics, extremely low viscosity, and excellent mass transfer properties of supercritical fluids. Under the infiltration of an scCO2 fluid, mesophase carbon microspheres (MCMB) are exfoliated into graphite flakes and achieve good interfacial fusion with silicon and Prussian blue during ball-milling. The Prussian blue is transformed into Fe3O4 by subsequent heat treatment under a nitrogen atmosphere, and Fe3O4 introduced in this way enhances the lithium-storage capacity, cycling stability, and rate performance significantly of Si/C anodes. As an anode for LIBs, the reversible capacity of Si/Fe3O4/C reaches 1363 mA h g–1 after 600 cycles at 1 A g–1. This study provides an idea for the design and fabrication of Si-based anode materials with high capacity and long cycle life.

Structures and transport properties of supercritical SiO2-H2O and NaAlSi3O8-H2O fluids

Abstract Speciation and transport properties of supercritical fluids is critical for understanding their behavior in the Earth’s interior. Here, we report a systematic first principles molecular dynamics simulation study of the structure, speciation, self-diffusivity (D), and viscosity (η) of SiO2 melt, NaAlSi3O8 melt, SiO2-H2O and NaAlSi3O8-H2O fluids at 2000–3500 K with 0–70 wt% H2O. Our calculations show that as the water content increases, the proportion of Q0 species (Qn species, where n is the number of bridging oxygens in an individual Si/Al-O polyhedra) increases while Q4 decreases. The proportions of Q1, Q2, and Q3 species first increase and then decrease with increasing water content. The diffusivity sequence for the supercritical SiO2-H2O fluids is DH >DO >DSi, and for the supercritical NaAlSi3O8-H2O fluids, on the whole, is DNa ≈ DH >DO >DAl ≈ DSi. The viscosities of the two systems decrease drastically at the beginning of the increase in water content, and then decrease slowly. We demonstrate that the exponential decrease in the viscosity of polymerized silicate melt with increasing water content is due to a sharp decrease in the proportion of Q4 species and increase in Si-O-H. The typical structural feature of supercritical fluid is that it contains a large amount of easy-to-flow partially polymerized or depolymerized protonated silicate units, which leads to a low viscosity while being enriched in silicate. This feature provides supercritical fluids the potential to transport elements that are hard to migrate in aqueous fluids or hydrous silicate melts, such as high field strength elements.

Preparation and Properties of Pulsed Composite Coatings of Supercritical Graphene Quantum Dots

Using graphene quantum dots with unique properties as the second phase additive and utilizing the high diffusion and transfer properties of supercritical fluids, Ni-based nanocomposite coatings were prepared by pulsed electrodeposition technology. The effects of the pulse duty cycle on the microstructure, mechanical properties, and corrosion resistance of composite coatings were investigated. The results showed that the graphene quantum dots are successfully embedded in the coatings, and under supercritical conditions, a suitable pulse duty cycle can improve the surface density and sphericity of the coatings. Raman spectroscopy and carbon-sulfur analyzer test indicated that supercritical conditions can improve the quality and content of graphene quantum dots in the coatings. The graphene quantum dots composite coating prepared when the pulse duty cycle is 0.3 has more excellent mechanical properties. Its microhardness is higher, and it has a smaller friction coefficient and wear scar cross-sectional area. Tafel polarization experiments indicated that under supercritical conditions, the corrosion current density of graphene quantum dots composite coating prepared when the pulse duty cycle is 0.3 is small, which is 1.286 × 10−5 A·cm−2. The 120 h immersion corrosion study showed that no obvious corrosion occurs on the surface. Therefore, its corrosion resistance is more excellent.

Supercritical transition mechanism of immiscible ethanol/hexadecane droplets

Although the properties of supercritical fluids have been significantly focused on, few studies have focused on the transition process of multicomponent fluids from the subcritical to supercritical state. Herein, the trans-critical behavior of an immiscible binary ethanol/hexadecane (EtOH/C16) droplet under supercritical nitrogen environments is analyzed for the first time using molecular dynamics. The ambient pressure (p) and ambient temperature (T) of the droplets exceed the critical conditions for both EtOH and C16. Moreover, trans-critical EtOH/C16 droplets undergo a two-stage bulging-to-shrinking process. Liquid fraction λ is introduced to quantify the structural characteristics of trans-critical fluids. Fluids inside the droplet are shown to transform from the vapor to liquid phase, signified by the increase in λ with p. Three droplet evolution types are classified based on p: micro-explosion, puffing, and mixing types. The occurrence of each trans-critical droplet evolution type is determined by the competition between the subcritical gasification of EtOH and the supercritical pseudo-boiling of C16. The supercritical transition of C16 can be detected under each condition, while that of EtOH only occurs for the mixing-type droplet evolution. Furthermore, a p–T diagram is provided to analyze the combined effect of T and p on the trans-critical droplet evolution types.

Thermodynamic and Transport Properties of Supercritical Fluids. Part 2: Review of Transport Properties

Thermodynamic and Transport Properties of Supercritical Fluids. Part 2: Review of Transport Properties

Optimization method of a novel airfoil fin heat exchanger based on the entransy dissipation theory

<p indent=0mm>The structure of the novel airfoil fin heat exchanger was optimized by the synergistic enhancement method based on the entransy matching performance, and two types of nonuniform fin distribution structures were proposed. The heat transfer and flow performance of various airfoil fin distribution structures were numerically studied by using supercritical CO₂ as the working medium under constant heat flux boundary conditions. The results showed that considering the extremely uneven distribution of heat transfer parameters arising from the drastic changes in the physical properties of supercritical fluid, the distribution of novel airfoil fins was changed under the condition that the total heat transfer area remained constant. The matching performance between the entransy of fluid and that of the wall heat flux was improved, and the distribution uniformity of the local entransy dissipation rate in the channel was improved. Hence, the total entransy dissipation rate in the channel was reduced, and the heat transfer performance was improved. The numerical studies under the boundary condition of variable heat flux in the two-fluid coupled heat transfer process showed that the distribution mode of the novel airfoil fins changed according to the distribution characteristics of heat transfer parameters in the two-fluid coupled heat exchanger. Under the condition that the total heat transfer area remained constant, the distribution matching of the entransy of hot and cold fluid also improved, so that the local entransy dissipation rate was more uniform in the heat transfer area, and the entransy dissipation rate was reduced. The entransy distribution-matching principle provides a new idea and method for the structural optimization and improvement of heat exchangers, which has important theoretical and engineering significance.

Simultaneously deposited Pt-alloy nanoparticles over graphene nanoplatelets via supercritical carbon dioxide deposition for PEM fuel cells

One of the main barriers to the commercialization of polymer electrolyte membrane fuel cell (PEMFC) systems is the cost, which is largely due to the need of platinum (Pt)-containing catalysts. In order to overcome this issue, several methods have been developed. One of them is the supported electrocatalysts prepared by combining a low cost second metal with Pt. Motivated by this idea, in this study, nano-sized Pt-M (M = Ni, Fe, Cu) binary electrocatalysts were synthesized on the graphene nanoplatelets (GNPs) via supercritical fluid deposition (SFD) technique in order to decrease the cost and increase the activity of the catalysts. Because, the unusual properties of supercritical fluids (SFs), including tunable solvent strength, high diffusivity, low viscosity, and low surface tension, offer significant advantages over conventional techniques for materials processing. In this regard, compared to the other SFs, carbon dioxide (CO2) has received much more attention due to its easy accessibility to the supercritical state, relative benignity to the environment, chemical inertness, low toxicity, low cost. The supercritical carbon dioxide (scCO2) deposition technique involves firstly the dissolution of the metal precursor onto the support material, and then conversion of the metal precursor to its metallic form by means of thermal or chemical conversion. Synthesis of supported bimetallic nanoparticles (NPs) via scCO2 can be sequentially or simultaneously. Herein, we investigated the development of Pt-M (PtCu, PtNi, PtFe) alloy NPs on GNPs by scCO2 deposition via simultaneous addition of metal precursors. Subsequently, these catalysts were characterized by employing various characterization techniques and systems such as X-Ray Diffaction (XRD), Thermogravimetric Analysis (TGA), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Transmission Electron Microscopy (TEM), Raman Spectroscopy, Cyclic Voltammetry (CV), Rotating Disk Electrode (RDE) and PEM Fuel Cell performance tests. The obtained results revealed the formation of bimetallic catalysts within the size ranges from 1.6 to 2.1 nm. Furthermore, CV results demonstrate that PtNi/GNPs catalyst exhibit significantly high catalytic activity toward the PEM fuel cell reaction in comparison with the PtFe/GNPs and PtCu/GNPs. Also, PtNi/GNPs catalyst show about 2–4 times higher durability than the PtFe/GNPs and PtCu/GNPs catalysts in the accelerated degradation tests (ADTs). All results suggested that the PtNi/GNPs catalyst has great potential for PEM fuel cell applications.

Applications of Supercritical Anti-Solvent Process in Preparation of Solid Multicomponent Systems.

Solid multicomponent systems (SMS) are gaining an increasingly important role in the pharmaceutical industry, to improve the physicochemical properties of active pharmaceutical ingredients (APIs). In recent years, various processes have been employed for SMS manufacturing. Control of the particle solid-state properties, such as size, morphology, and crystal form is required to optimize the SMS formulation. By utilizing the unique and tunable properties of supercritical fluids, supercritical anti-solvent (SAS) process holds great promise for the manipulation of the solid-state properties of APIs. The SAS techniques have been developed from batch to continuous mode. Their applications in SMS preparation are summarized in this review. Many pharmaceutical co-crystals and solid dispersions have been successfully produced via the SAS process, where the solid-state properties of APIs can be well designed by controlling the operating parameters. The underlying mechanisms on the manipulation of solid-state properties are discussed, with the help of on-line monitoring and computational techniques. With continuous researching, SAS process will give a large contribution to the scalable and continuous manufacturing of desired SMS in the near future.

Thermodynamic and Transport Properties of Supercritical Fluids: Review of Thermodynamic Properties (Part 1)

This review presents the results of a detailed analysis of the role of isochoric heat capacity as a key thermodynamic property of matter in the investigation of critical and supercritical phenomena. A brief historical background is given on the role and contribution of Russian scientific schools to the experimental investigation of the isochoric heat capacity in the critical region in the development of the nonclassical (scaling) theory of critical phenomena, which drastically changed the understanding of the physical nature of critical and supercritical phenomena. The experimental behavior of the isochoric heat capacity and other thermodynamic properties of fluids in the critical and supercritical regions related to it is investigated in detail. The role of new experimental studies of two-phase isochoric heat capacity near the critical point in the development of a “complete” scaling theory is discussed. This theory allows us to understand the physical nature of the asymmetry of the liquid–gas coexistence curve near the critical point and to estimate the contribution of the chemical potential to the divergence of the two-phase isochoric heat capacity at the critical point. The review also focuses on supercritical phase transitions and the role of isochoric heat capacity in determining the Widom line, which separates the liquid-like and gas-like regions in supercritical states; i.e., it defines the boundaries of the coexistence of liquid-like and gas-like phases in supercritical fluids.

Sequential extraction of carnosic acid, rosmarinic acid and pigments (carotenoids and chlorophylls) from Rosemary by online supercritical fluid extraction-supercritical fluid chromatography

A high degree of selectivity is required during the plant extraction process in order to obtain extracts enriched in specific compounds or to avoid the extraction of unwanted ones. Rosemary is well known for its antioxidant compounds (carnosic acid, carnosol and rosmarinic acid). The plant also contains pigments (i.e. carotenoids, chlorophylls) which may cause a colour problem during the use of the extract in cosmetic formulations, for example. Supercritical fluid extraction is considered as a selective technique for plant extraction. Due to the physico-chemical properties of supercritical fluids, related to pressure, temperature and modifier addition, it is possible to carry out sequential extraction with successive conditions to collect different fractions that are rich either in pigments or in bioactive compounds.The aim of this study was to selectively extract bioactive compounds (i.e. carnosic acid and rosmarinic acid) and pigments (carotenoids and chlorophylls) from rosemary using supercritical fluid extraction. The optimisation of the extraction method was carried out using supercritical fluid extraction online coupled with a supercritical fluid chromatography (SFE-SFC) system. Two columns of different polarities were coupled to achieve the separation of the targeted compounds every five minutes during the extraction.Four fractions were obtained: a first one rich in carotenoids obtained with pure CO2 (25°C and 20 MPa), a second rich in carnosic acid obtained with 3% polar modifier (EtOH:water 50/50 v/v), a third fraction rich in rosmarinic acid using 10% of the same modifier and a fourth fraction rich in chlorophylls with 30% of ethanol as modifier. These four samples were then analysed by UHPLC-DAD-ESI-QTOF-HRMS in order to identify other extracted compounds and to study how the selected conditions impacted their extraction.

A molecular simulation study on solvation free energy and structural properties of polycyclic aromatic hydrocarbons in supercritical water environment

Molecular simulations have been successfully applied for studying the kinetic properties of supercritical fluids, extremely in exploring the microscopic mechanisms of high-pressure and high-temperature fluids. Molecular simulation is an efficient and convenient way to investigate complex molecular systems with supercritical water. Polycyclic aromatic hydrocarbons (PAHs) are typical coal chemical pollutants. Molecular simulations using PAH model compounds were carried out to explore the effects of supercritical water on solvation free energies and structural properties. The water density was ranging from 0.1 g/cm3 to 0.3 g/cm3 and temperature was increased from 380 °C to 440 °C. In terms of PAHs in this study, the simulations and calculations revealed that the solvation free energy remained negative and simultaneously varied with water density and temperature. This work is expected to provide a theoretical support for understanding the dynamic, structural properties and the solvation properties of different aromatic hydrocarbons in supercritical water environment.

Supercritical Fluid Applications in the Design of Novel Antimicrobial Materials.

Bacterial resistance to antibiotics is one of the biggest problems in the modern world. The prevention of bacterial spreading from hospitals to the community and vice versa is an issue we have to deal with. This review presents a vast potential of contemporary high-pressure techniques in the design of materials with antimicrobial activity. Scientists from all over the world came up with ideas on how to exploit extraordinary properties of supercritical fluids in the production of advantageous materials in an environmentally friendly way. The review summarizes reported methods and results.

Physical Supercritical Fluid Deposition: Patterning Solution Processable Materials on Curved and Flexible Surfaces.

We provide the initial demonstration of a general thin film deposition technique that leverages the unique solubility properties of supercritical fluids. The technique is the solution-phase analogue of physical vapor deposition and allows thin films of a semiconducting polymer to be grown without the need for in situ chemical reactions. Film growth is approximately linear with time, indicating that film thickness can be controlled in a straightforward manner by varying the time of deposition. To further demonstrate the flexibility of the technique, we demonstrate precise control over the location of material deposition using a combination of photolithography and resistive heating. The potential for scalable manufacturing is demonstrated by use of a master to control deposition onto a flexible polymer film. Finally, we demonstrate a unique deposition capability of this technique by depositing patterns onto the curved interior of a hemisphere made from a silicone elastomer. This capability is not possible with any printing or line-of-sight deposition technique. More generally, the ability to control the deposition of solution processed materials with high accuracy provides the long sought after bridge between top-down and bottom-up self-assembly.

Gas or Liquid? The Supercritical Behavior of Pure Fluids.

By definition, the distinction between a gas and a liquid ceases to exist beyond the critical point for pure fluids. Nevertheless, there remains a strong desire to attribute gas-like or liquid-like behavior to fluids corresponding to different parts of the supercritical region, especially as this becomes important for understanding and designing the properties of supercritical fluids. Here, we use a combination of fluctuation solution theory and accurate equation of state data to elucidate an easily accessible dividing line and corresponding transition regime between liquid-like and gas-like behavior in the supercritical region of all pure fluids. Liquid-like behavior in the supercritical region is characterized by a negative skewness in the particle number distribution for an equivalent open system, indicating that particle deletion is favored for liquids, whereas gas-like behavior is characterized by a positive skewness, indicating that particle insertion is favored for gases. Identical behavior is observed either side of the liquid-vapor line. The possible consequences for the behavior of fluids at the critical point are also discussed.

Accurate prediction of thermal conductivity of supercritical propane using LSSVM

ABSTRACT Recently supercritical fluids have found impressive applications in different industries. According to this, researchers have been interested to study thermophysical properties of supercritical fluids. Due to high price and time consuming process of experiments related to supercritical condition, the attention to computational study were increased. In present contribution, a new LSSVM-GA model were proposed to estimate the thermal conductivity of supercritical propane. The thermal conductivity data were extracted from open literature. By Applying LSSVM-GA on 380 data points and finding optimum parameters, the estimated values of thermal conductivity of supercritical propane were compared with experimental data and it was confirmed that the predictive modeling performed in acceptable manner based on reported errors and fitting parameters. Consequently, the model is reliable that can be utilized to forecast the thermal conductivity of supercritical propane.

Supercritical CO2: Properties and Technological Applications - A Review

The main goal of the present paper is to assess the available information so as to obtain a general procedure for dealing with the critical enhancement of the thermodynamic and transport properties of supercritical CO2 and CO2 containing binary mixtures for practical and scientific applications. The present review provides comprehensive analysis of the thermodynamic and transport properties of supercritical carbon dioxide and CO2 containing binary mixtures (experiment and theory) and their various technological and scientific applications in different natural and industrial processes. The available information for the thermodynamic and transport properties (experiment and theory) enhancement (anomaly) of supercritical carbon dioxide and SC CO2 + solute mixtures is comprehensively reviewed. The effect of long-range order parameter fluctuations on the thermodynamic and transport properties of supercritical fluids (SC CO2) will be discussed. Simplified scaling type equation based on mode-coupling theory of critical dynamics with two critical amplitudes and one cutoff wave number as fluid-specific parameters was used to accurately predict of the transport properties of supercritical carbon dioxide. The recommended values of the specific parameters (asymptotic critical amplitudes) of the carbon dioxide for practical (prediction of the thermodynamic and transport properties of the supercritical CO2 for technological applications) and scientific use were provided. The role of the critical line shapes of the carbon dioxide containing binary mixture (SC CO2+solvent) in determination of the critical behavior of the mixture near the critical point of pure supercritical solvent (CO2) is discussed. Krichevskii parameter concept for a description of thermodynamic behavior of dilute near-critical SC CO2+solute mixtures is also discussed. The structural and thermodynamic properties of the carbon dioxide containing binary mixtures near the critical point of pure solvent (CO2) are discussed.

Microencapsulation and Nanoencapsulation Using Supercritical Fluid (SCF) Techniques.

The unique properties of supercritical fluids, in particular supercritical carbon dioxide (CO2), provide numerous opportunities for the development of processes for pharmaceutical applications. One of the potential applications for pharmaceuticals includes microencapsulation and nanoencapsulation for drug delivery purposes. Supercritical CO2 processes allow the design and control of particle size, as well as drug loading by utilizing the tunable properties of supercritical CO2 at different operating conditions (flow ratio, temperature, pressures, etc.). This review aims to provide a comprehensive overview of the processes and techniques using supercritical fluid processing based on the supercritical properties, the role of supercritical carbon dioxide during the process, and the mechanism of formulation production for each process discussed. The considerations for equipment configurations to achieve the various processes described and the mechanisms behind the representative processes such as RESS (rapid expansion of supercritical solutions), SAS (supercritical antisolvent), SFEE (supercritical fluid extraction of emulsions), PGSS (particles from gas-saturated solutions), drying, and polymer foaming will be explained via schematic representation. More recent developments such as fluidized bed coating using supercritical CO2 as the fluidizing and drying medium, the supercritical CO2 spray drying of aqueous solutions, as well as the production of microporous drug releasing devices via foaming, will be highlighted in this review. Development and strategies to control and optimize the particle morphology, drug loading, and yield from the major processes will also be discussed.